Odd−Even Effect in Free Radical Polymerization of Optically Active 2,5-Bis[(4‘-alkoxycarbonyl)- phenyl]styrene

Zhi, Junge; Zhu, Zhiguo; Liu, Anhua; Cui, Jiaxi; Wan, Xinhua; Zhou, Qifeng

doi:10.1021/ma8000115

Cited by 56 publications

(51 citation statements)

References 53 publications

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“…This can be attributed to the unique structures of MJLCPs in which mesogens are oriented preferentially perpendicular to the main chain. In addition, monomers containing optically active groups [67][68][69] and chromophoric groups 20 have been designed and synthesized. Some have been polymerized by living methods, whereas some not yet.…”

Section: Discussionmentioning

confidence: 99%

Jacketed polymers: Controlled synthesis of mesogen‐jacketed polymers and block copolymers

Gao

Fan

Shen

et al. 2008

J. Polym. Sci. A Polym. Chem.

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The controlled radical polymerization of mesogen‐jacketed liquid crystalline polymers has triggered great interests in synthesis of complex structures as well as well‐defined linear homopolymers with controlled molecular weight and narrow molecular weight distributions. This review highlights the synthetic strategies of controlled radical polymerization of linear homopolymers, star polymers, superbranched polymers, graft polymers, block copolymers, star block copolymers, and so on. The employed living methods include nitroxide‐mediated radical polymerization and atom transfer radical polymerization. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 319–330, 2009

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Section: Discussionmentioning

confidence: 99%

Jacketed polymers: Controlled synthesis of mesogen‐jacketed polymers and block copolymers

Gao

Fan

Shen

et al. 2008

J. Polym. Sci. A Polym. Chem.

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“…Recently, we reported the odd–even effect in free radical polymerization of chiral monomers, S ‐(+)‐Mm/ R ‐(−)‐M0 (Chart ) and S ‐(+)‐HexMm / R ‐(−)‐HexM0, S ‐(+)‐MmHex / R ‐(−)‐M0Hex ( Chart ) . The stereogenic centers in the monomers can transfer their chiral messages to the polymer main chains over a long distance during radical polymerization through the steric interaction between the side group on the propagation end and that of the incoming monomer.…”

Section: Introductionmentioning

confidence: 99%

Long range chirality transfer in free radical polymerization of vinylterphenyl monomers bearing chiral alkoxy groups

Liu

Zhao

Wang

et al. 2013

J. Polym. Sci. Part A: Polym. Chem.

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Two series of chiral bulky vinyl aromatics, 2-(4'-alkoxyphenyl)-5-(4'-hexyloxyphenyl)styrene (S-Am (m 5 0, 1, 2, 3)/R-A0) and 2-(4'-hexyloxyphenyl)-5-(4'-alkoxyphenyl)styrene (S-Bm (m 5 0, 1, 2, 3)/R-B0), were synthesized and radically polymerized (where m denotes the carbon number between stereogenic center and ether oxygen atom). The generation and stereomutation of helical structures as well as chirality transfer from the stereogenic center of the side-group to the polymer backbone during polymerization were investigated by a combination of 1 H-and 13 C-NMR, polarimetry, circular dichroism spectroscopy, liquid crystal induced circular dichroism, and computer simulation. All the polymers, except S-B3, display optical rotations and Cotton effects in the UV-Vis absorption region of terphenyl pendant, which are quite different from the corresponding model compounds and monomers, suggesting the formation of chiral secondary structures, that is, skewed packing of side-groups and twisting of polymer backbones with a dominant screw sense. The sign of optical rotation changes alternatively and the strength diminishes when m increases from 1 to 3. However, although the stereogenic centers in S-A0 and S-B0 are closer to the vinyl group than those in S-A1 and S-B1, separately, a weaker chiral induction power is observed. Moreover, optical rotations of polymers derived from S-A0/R-A0 and S-B0/ R-B0 are opposite in sign and increase with annealing time in tetrahydrofuran. These results are in a sharp contrast with our previous findings in similar vinylterphenyl compounds, where -COO-rather than -O-links the chiral alkyl tail to the terphenyl group, manifesting a remarkable effect of small structural variation of side-group on polymer chiroptical properties and complexity of chirality transfer in helix-sense-selective polymerization.

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“…Artificial helical polymers possessing well‐organized catalytic sites may act as enzymes in asymmetric catalysis, but are outstanding for their facile preparation and tolerability of organic solvents. Until now, many categories of synthetic helical polymers have been available, such as poly(methacrylate)s, poly(acetylene)s, poly(isocyanide)s, poly(isocyanate)s, polyguanidines, polysilanes, and poly(vinylterphenyl)s . Some of them have demonstrated potential uses in asymmetric catalysis.…”

Section: Chartmentioning

confidence: 99%

Synthesis and Properties of a Novel Pyridineoxazoline Containing Optically Active Helical Polymer as a Catalyst Ligand for Asymmetric Diels–Alder Reaction

Wang

Zhang

et al. 2015

Chirality

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A novel pyridineoxazoline (PyOx) containing helical polymer, poly{(-)-(S)-4-tert-butyl-2-[5-(4-tert-butylphenyl)-3-vinylpyridin-2-yl]-oxazoline} (PA), was designed and synthesized to approach the effect of chain conformation on the catalytic property. Its complex with Cu(OTf)(2) , i.e., Cu(II)-PA, was employed to catalyze the homogeneous Diels-Alder (D-A) reaction of alkenoyl pyridine N-oxides with cyclopentadiene in tetrahydrofuran. Compared with the previously reported copper complex, Cu(II)-P1 (RSC Advances, 2015, 5, 2882), which was derived from a nonhelical poly[(-)-(S)-4-tert-butyl-2-(3-vinylpyridin-2-yl)-oxazoline], Cu(II)-PA exhibited a remarkably enhanced enantioselectivity and reaction rate. However, its enantioselectivity was lower than the Cu(II) complex of (-)-(S)-4-tert-butyl-2-[5-(4-tert-butylphenyl)-3-vinylpyridin-2-yl]-oxazoline (Cu(II)-A), a low molar mass model compound.

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Odd−Even Effect in Free Radical Polymerization of Optically Active 2,5-Bis[(4‘-alkoxycarbonyl)- phenyl]styrene

Abstract: Optically active polymers with main-chain helical chiralities have attracted long-standing interest for their wide potential applications in asymmetric synthesis, molecular recognition, and photoelectrical materials.

Cited by 56 publications

References 53 publications

Jacketed polymers: Controlled synthesis of mesogen‐jacketed polymers and block copolymers

Jacketed polymers: Controlled synthesis of mesogen‐jacketed polymers and block copolymers

Long range chirality transfer in free radical polymerization of vinylterphenyl monomers bearing chiral alkoxy groups

Synthesis and Properties of a Novel Pyridineoxazoline Containing Optically Active Helical Polymer as a Catalyst Ligand for Asymmetric Diels–Alder Reaction

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